Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
  • C07C251/72—Hydrazones
  • C07C251/88—Hydrazones having also the other nitrogen atom doubly-bound to a carbon atom, e.g. azines
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

• This invention relates to the production of ketazines.
• R 1 + r 2 and R 3 + R 4 individually is alkylene of 5 to 10 carbon atoms
• the radicals R 1 to R 4 preferably represent linear or branched alkyl radicals with from 1 to 4 carbon atoms, such as, for example methyl, ethyl, propyl, i-propyl or butyl; cycloalkyl radicals with from 5 to 7 carbon atoms such as, for example, cyclopentyl or cyclohexyl; aralkyl radicals with from 7 to 9 carbon atoms, for example benzyl; alkylene radicals with from 5 to 7 carbon atoms such as, for example, pentamethylene or hexamethylene; or aryl radicals with from 6 to 9 carbon atoms such as, for example, phenyl, p-chlorophenyl, p-methyl phenyl or o-methoxy phenyl.
• Oxaziridines of formula (II) suitable for use in the process according to the invention are, for example, 3,3-dimethyl oxaziridine 3,3-methyl ethyl oxaziridine, 3,3-diethyl oxaziridine, 3,3-methyl phenyl oxaziridine 3,3-methyl isopropyl oxaziridine, 3,3-cyclohexyl-n-propyl oxaziridine 3,3-hexamethylene oxaziridine, and the like. They are produced by known methods [ Chem. Ber. 100, 2593 (1967); Angew. Chemie. 76, 197 (1964); Chem. Ber. 99, 3233 (1966)].
• ketones may for example, be used as ketones corresponding to formula (III): acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, methyl phenyl ketone, cyclohexanone and cycloheptanone.
• equation (1) it is possible to obtain symmetrical and asymmetrical ketazines when, on the one hand, the radicals R 3 and R 4 are the same as R 1 and R 2 and, on the other hand, when the radicals R 3 or R 4 are different from R 1 and R 2 .
• the ketones can be used in pure form or in solution in an organic solvent.
• Ammonia may be used in gaseous form or in the form of concentrated aqueous solutions containing about 5 to 30% by weight of NH 3 .
• the reaction is best carried out in solution because the oxaziridines are unstable in pure form.
• solvents which are stable with respect to the reactants and those solvents used in the production of the oxaziridines are possible to use solvents which are stable with respect to the reactants and those solvents used in the production of the oxaziridines.
• Suitable solvents are linear or branched hydrocarbons with up to 12 carbon atoms, lower halogenated hydrocarbons or halogenated derivatives of benzene and alcohols with from 5 to 10 carbon atoms.
• suitable solvents include benzene, toluene, xylenes, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, chlorotoluene, amyl alcohol, hexanol, 2-ethyl hexanol, 3,5,5-trimethyl hexanol or decanols.
• the process according to the invention is carried out by reacting the oxaziridines of formula (II) in solution in an organic solvent with ammonia in the presence of the ketones of formula (III).
• the reaction is carried out by introducing gaseous ammonia or ammonia in the form of an aqueous solution into a mixture of oxaziridines (II) and ketones (III), or by introducing ammonia and ketone (III) simultaneously into the oxaziridine solution, or by introducing only the ammonia to begin with and then, on completion of the reaction, the ketone (III) into the reaction mixture.
• the reaction may be carried out under normal pressure, or under an excess pressure of up to about 10 atmospheres if it is necessary to keep the excess ammonia in solution.
• the molar ratio of oxaziridine (II) to ammonia can be in the range of about 1 : 1 to 1 : 100, a molar ratio of about 1 : 2 to 1 : 20 being preferred.
• the molar ratio of oxaziridine (II) to ketone (III) can be in the range of about 1 : 0.5 to 1 : 20, although a molar ratio of about 1 : 1 to 1 : 5 is preferred.
• the concentration of oxaziridine in organic solvents can be about 0.01 to 10 moles per liter and is preferably about 0.1 to 5 moles per liter, the range from 0.5 to 3 moles per liter being the most suitable.
• the reaction temperature can be in the range of about -20° to +100°C, temperatures in the range of about 0°C to 70°C being preferred.
• the reaction temperature is governed primarily by the boiling point of the solvent and by the concentration of ammonia.
• the reaction may be carried out continuously or in batches and is best carried out immediately after preparation of the oxaziridine.
• the ketazines obtained by the process according to the invention can be used for the production of hydrazine hydrate by hydrolysis using known methods, or, by means of acids, for the production of hydrazine salts accompanied by liberation of the ketones.
• methylene chloride solution containing 0.0588 mole of 3,3-dimethyl oxyziridine are dried over sodium sulfate, and concentrated under normal pressure to approximately 10 ml in a 40 cm Raschig column with a reflux ratio of 3 : 1.
• a solution containing approximately 1.8 moles of 3,3-dimethyl oxaziridine per liter of methylene chloride together with unreacted acetone is obtained for a distillation yield of 78%.
• Acetone-free oxaziridine solutions are prepared by distillation in the presence of a higher-boiling solvent, for example 1,2-dichloroethane.
• Gaseous ammonia is introduced at a temperature of 20°C up to the saturation point into 250 ml of a solution of the oxaziridines in toluene containing 0.05 mole of ketone.
• the gaseous ammonia is introduced at a rate of 20 liters per hour.
• the ketazines formed are quantitatively determined by titration. The results are set out in Table 2 below.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=5911347

Family Applications (1)

Country Status (5)

Citations (2)

• 1974
  • 1974-03-27 DE DE2414802A patent/DE2414802C2/de not_active Expired
• 1975
  • 1975-03-06 US US05/556,036 patent/US3965097A/en not_active Expired - Lifetime
  • 1975-03-24 GB GB12096/75A patent/GB1479850A/en not_active Expired
  • 1975-03-25 JP JP3502975A patent/JPS5725027B2/ja not_active Expired
  • 1975-03-27 FR FR7509769A patent/FR2265729B1/fr not_active Expired

Patent Citations (2)

Non-Patent Citations (3)

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